Process for Producing Paraxylene by Methylation of Benzene and/or Toluene

ABSTRACT

A process is described for producing paraxylene, in which an aromatic hydrocarbon feedstock comprising benzene and/or toluene is contacted with an alkylating reagent comprising methanol and/or dimethyl ether in an alkylation reaction zone under alkylation conditions in the presence of an alkylation catalyst to produce an alkylated aromatic product comprising xylenes. The alkylation catalyst comprises a molecular sieve having a Constraint Index≤5, and the alkylation conditions comprise a temperature less than 500° C. Paraxylene may then be recovered from the alkylated aromatic product.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of and claims the benefit of U.S.patent application Ser. No. 15/702,337, filed Sep. 12, 2017, which, inturn, claims benefit of U.S. Provisional Patent Application Ser. No.62/405,036 filed Oct. 6, 2016, the content of both of which are herebyincorporated herein by reference in their entirety.

FIELD

This disclosure relates to a process for the methylation of benzeneand/or toluene to produce xylenes, particularly paraxylene.

BACKGROUND

Xylenes are valuable precursors in the chemical industry. Of the threexylene isomers, paraxylene is the most important since it is a startingmaterial for manufacturing terephthalic acid, which is itself a valuableintermediate in the production of synthetic polyester fibers, films, andresins. Currently, the demand for paraxylene is growing at an annualrate of 5-7%.

One known route for the manufacture of paraxylene is by the methylationof benzene and/or toluene. For example, U.S. Pat. No. 6,504,072discloses a process for the selective production of paraxylene whichcomprises reacting toluene with methanol under alkylation conditions inthe presence of a catalyst comprising a porous crystalline materialhaving a Diffusion Parameter for 2,2 dimethylbutane of about 0.1-15sec⁻¹ when measured at a temperature of 120° C. and a 2,2 dimethylbutanepressure of 60 torr (8 kPa). The porous crystalline material ispreferably a medium-pore zeolite, particularly ZSM-5, which has beenseverely steamed at a temperature of at least 950° C. The alkylationconditions include a temperature between about 500 and 700° C., apressure of between about 1 atmosphere and 1000 psig (100 and 7000 kPa),a weight hourly space velocity between about 0.5 and about 1000 and amolar ratio of toluene to methanol of at least about 0.2.

In addition, U.S. Pat. No. 6,642,426 discloses a process for alkylatingan aromatic hydrocarbon reactant, especially toluene, with an alkylatingreagent comprising methanol to produce an alkylated aromatic product,comprising: introducing the aromatic hydrocarbon reactant into a reactorsystem at a first location, wherein the reactor system includes afluidized bed reaction zone comprising a temperature of 500 to 700° C.and an operating bed density of about 300 to 600 kg/m³, for producingthe alkylated aromatic product; introducing a plurality of streams ofsaid alkylating reactant directly into said fluidized bed reaction zoneat positions spaced apart in the direction of flow of the aromatichydrocarbon reactant, at least one of said streams being introduced at asecond location downstream from the first location; and recovering thealkylate aromatic product, produced by reaction of the aromatic reactantand the alkylating reagent, from the reactor system. The preferredcatalyst is ZSM-5 which has been selectivated by high temperaturesteaming.

As exemplified by the prior art discussed above, current processes forthe alkylation of benzene and/or toluene with methanol are conducted athigh temperatures, i.e., between 500 to 700° C. in the presence of amedium pore size zeolite, particularly ZSM-5. This results in a numberof problems, particularly in that catalyst life per cycle is relativelyshort and so frequent regeneration of the catalyst is required. Inaddition, the existing processes typically result in significantquantities of methanol being converted to ethylene and other lightolefins which reduces the yield of desirable products, such as xylenes,and increases recovery costs.

There is therefore a need for an improved process for the alkylation ofbenzene and/or toluene with methanol (or dimethyl ether), whichincreases catalyst cycle life and reduces gas make.

SUMMARY

According to the present disclosure, it has now been found that byconducting the alkylation reaction under relatively mild conditions,namely a temperature less than 500° C., in the presence of a large poresize or equivalent molecular sieve, benzene and/or toluene can bealkylated with methanol and/or dimethyl ether to produce xylenes withless light gas by-products and longer catalyst cycle life thanconventional high temperature processes. Methanol utilization (i.e.,percentage conversion of methanol to xylenes) is also improved ascompared to conventional high temperature processes.

Thus, in an embodiment, a process for producing paraxylene is providedin which an aromatic hydrocarbon feed comprising benzene and/or tolueneis contacted with an alkylating reagent comprising methanol and/ordimethyl ether in at least one alkylation reaction zone in the presenceof alkylation catalyst comprising a molecular sieve having a ConstraintIndex less than or equal to 5 and under alkylation conditions comprisinga temperature less than 500° C. to produce an alkylated aromatic productcomprising xylenes. Paraxylene may then be recovered from the alkylatedaromatic product.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of toluene and methanol conversion against time onstream in the process of alkylating toluene with methanol described inExample 1.

FIG. 2 is a graph of product selectivity against time on stream in theprocess of alkylating toluene with methanol described in Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Embodiments disclosed herein provide alkylation processes for producingxylenes, particularly paraxylene, that can be conducted under relativelymild conditions to produce xylenes with less light gas by-products andlonger catalyst cycle life than conventional high temperature processes.Methanol utilization (i.e., percentage conversion of methanol toxylenes) is also improved. In the inventive process, an aromatichydrocarbon feed comprising benzene and/or toluene is contacted with analkylating reagent comprising methanol and/or dimethyl ether in at leastone alkylation reaction zone in the presence of alkylation catalystunder alkylation conditions. The alkylation catalyst comprises amolecular sieve having a Constraint Index less than 5, such as less than4, for example less than 3, or in some embodiments less than 2, and thealkylation conditions comprise a temperature less than 500° C.

The process is effective to convert the benzene and/or toluene toxylenes with essentially 100% methanol conversion and substantially nolight gas make. The high methanol utilization is surprising in light ofthe methanol utilization in the prior art toluene and/or benzenemethylation processes, and results in the substantial advantages of lesscoke formation, which increases the catalyst life. Furthermore, in priorart processes, it is preferred to co-feed steam into the reactor withthe methanol to minimize the methanol side reactions, and the steamnegatively impacts catalyst life. With the nearly 100% methanolutilization in the inventive process, there is no need to co-feed steam,decreasing the energy demands of the process and increasing catalystlife.

The selectivity to xylenes in the inventive process is typically on theorder of 80%, with the main by-products being benzene and C₉₊ aromatics.The benzene can be separated from the alkylation effluent and recycledback to the alkylation reaction zone(s), while the C₉₊ aromatics can beseparated for blending into the gasoline pool or transalkylated withadditional benzene and/or toluene to make additional xylenes. The lifeof the alkylation catalyst is enhanced as compared with existingprocesses since methanol decomposition is much less at the lowerreaction temperature. Moreover, the use of a larger pore molecular sieveminimizes diffusion limitations and allows the alkylation to be carriedout at commercially viable WHSVs.

As used herein, the term “C_(n)” hydrocarbon wherein n is a positiveinteger, e.g., 1, 2, 3, 4, 5, etc, means a hydrocarbon having n numberof carbon atom(s) per molecule. The term “C_(n+)” hydrocarbon wherein nis a positive integer, e.g., 1, 2, 3, 4, 5, etc, means a hydrocarbonhaving at least n number of carbon atom(s) per molecule. The term“C_(n−)” hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4,5, etc, as used herein, means a hydrocarbon having no more than n numberof carbon atom(s) per molecule.

As used herein, the terms “alkylating” and “methylating”, or“alkylation” and “methylation” may be used interchangeably.

Constraint Index is a convenient measure of the extent to which amolecular sieve provides control of molecules of varying sizes to itsinternal structure. The method by which Constraint Index is determinedis described fully in U.S. Pat. No. 4,016,218, which is incorporatedherein by reference for details of the method.

Examples of suitable molecular sieves having a Constraint Index lessthan 5 suitable for use in the present process comprise zeolite beta,zeolite Y, Ultrastable Y (USY), Ultrahydrophobic Y (UHP-Y), DealuminizedY (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-12, ZSM-14, ZSM-18, ZSM-20 andmixtures thereof. Zeolite ZSM-3 is described in U.S. Pat. No. 3,415,736.Zeolite ZSM-4 is described in U.S. Pat. No. 4,021,947. Zeolite ZSM-12 isdescribed in U.S. Pat. No. 3,832,449. Zeolite ZSM-14 is described inU.S. Pat. No. 3,923,636. Zeolite ZSM-18 is described in U.S. Pat. No.3,950,496. Zeolite ZSM-20 is described in U.S. Pat. No. 3,972,983.Zeolite Beta is described in U.S. Pat. No. 3,308,069, and Re. No.28,341. Low sodium Ultrastable Y molecular sieve (USY) is described inU.S. Pat. Nos. 3,293,192 and 3,449,070. Ultrahydrophobic Y (UHP-Y) isdescribed in U.S. Pat. No. 4,401,556. Dealuminized Y zeolite (Deal Y)may be prepared by the method found in U.S. Pat. No. 3,442,795. ZeoliteY and mordenite are naturally occurring materials but are also availablein synthetic forms, such as TEA-mordenite (i.e., synthetic mordeniteprepared from a reaction mixture comprising a tetraethylammoniumdirecting agent). TEA-mordenite is disclosed in U.S. Pat. Nos. 3,766,093and 3,894,104.

One preferred class of molecular sieve suitable for use in the presentprocess, and having a Constraint Index less than 5, are crystallinemicroporous materials of the MWW framework type. As used herein, theterm “crystalline microporous material of the MWW framework type”includes one or more of:

molecular sieves made from a common first degree crystalline buildingblock unit cell, which unit cell has the MWW framework topology. (A unitcell is a spatial arrangement of atoms which if tiled inthree-dimensional space describes the crystal structure. Such crystalstructures are discussed in the “Atlas of Zeolite Framework Types”,Fifth edition, 2001, the entire content of which is incorporated asreference);

molecular sieves made from a common second degree building block, beinga 2-dimensional tiling of such MWW framework topology unit cells,forming a monolayer of one unit cell thickness, preferably one c-unitcell thickness;

molecular sieves made from common second degree building blocks, beinglayers of one or more than one unit cell thickness, wherein the layer ofmore than one unit cell thickness is made from stacking, packing, orbinding at least two monolayers of MWW framework topology unit cells.The stacking of such second degree building blocks can be in a regularfashion, an irregular fashion, a random fashion, or any combinationthereof; and

molecular sieves made by any regular or random 2-dimensional or3-dimensional combination of unit cells having the MWW frameworktopology.

Crystalline microporous materials of the MWW framework type includethose molecular sieves having an X-ray diffraction pattern includingd-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07Angstrom. The X-ray diffraction data used to characterize the materialare obtained by standard techniques using the K-alpha doublet of copperas incident radiation and a diffractometer equipped with a scintillationcounter and associated computer as the collection system.

Examples of crystalline microporous materials of the MWW framework typeinclude MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (describedin U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No.4,826,667), ERB-1 (described in European Patent No. 0293032), ITQ-1(described in U.S. Pat. No. 6,077,498), ITQ-2 (described inInternational Publication No. WO97/17290), MCM-36 (described in U.S.Pat. No. 5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575),MCM-56 (described in U.S. Pat. No. 5,362,697), UZM-8 (described in U.S.Pat. No. 6,756,030), UZM-8HS (described in U.S. Pat. No. 7,713,513),UZM-37 (described in U.S. Pat. No. 7,982,084), EMM-10 (described in U.S.Pat. No. 7,842,277), EMM-12 (described in U.S. Pat. No. 8,704,025),EMM-13 (described in U.S. Pat. No. 8,704,023), MIT-1 (described by Luoet. al, in Chemical Science, 2015, Vol. 6, pp. 6320-6324) and mixturesthereof, with MCM-49 generally being preferred.

In some embodiments, the crystalline microporous material of the MWWframework type employed herein may be contaminated with othercrystalline materials, such as ferrierite or quartz. These contaminantsmay be present in quantities≤10% by weight, normally ≤5% by weight.

Additionally or alternatively, the molecular sieves useful herein may becharacterized by a ratio of silicon to aluminum. In particularembodiments, the molecular sieves suitable herein include those having aSi/Al ratio of less than 100, preferably about 15 to 50.

In some embodiments, the molecular sieves employed herein are notsubjected to pre-treatments, such as high temperature steaming, tomodify their diffusion properties. In other embodiments, the molecularsieves may be selectivated, either before introduction into thearomatization reactor or in-situ in the reactor, by contacting thecatalyst with a selectivating agent, such as silicon, steam, coke, or acombination thereof. In one embodiment, the catalyst issilica-selectivated by contacting the catalyst with at least oneorganosilicon in a liquid carrier and subsequently calcining thesilicon-containing catalyst in an oxygen-containing atmosphere, e.g.,air, at a temperature of 350 to 550° C. A suitable silica-selectivationprocedure is described in U.S. Pat. No. 5,476,823, the entire contentsof which are incorporated herein by reference. In another embodiment,the catalyst is selectivated by contacting the catalyst with steam.Steaming of the zeolite is effected at a temperature of at least about950° C., preferably about 950 to about 1075° C., and most preferablyabout 1000 to about 1050° C., for about 10 minutes to about 10 hours,preferably from 30 minutes to 5 hours. The selectivation procedure,which may be repeated multiple times, alters the diffusioncharacteristics of the molecular sieve and may increase the xyleneyield.

In addition to, or in place of, silica or steam selectivation, thecatalyst may be subjected to coke selectivation. This optional cokeselectivation typically involves contacting the catalyst with athermally decomposable organic compound at an elevated temperature inexcess of the decomposition temperature of said compound but below thetemperature at which the crystallinity of the molecular sieve isadversely affected. Further details regarding coke selectivationtechniques are provided in the U.S. Pat. No. 4,117,026, incorporated byreference herein. In some embodiments, a combination of silicaselectivation and coke selectivation may be employed.

It may be desirable to combine the molecular sieve, prior toselectivating, with at least one oxide modifier, such as at least oneoxide selected from elements of Groups 2 to 4 and 13 to 16 of thePeriodic Table. Most preferably, said at least one oxide modifier isselected from oxides of boron, magnesium, calcium, lanthanum, and mostpreferably phosphorus. In some cases, the molecular sieve may becombined with more than one oxide modifier, for example a combination ofphosphorus with calcium and/or magnesium, since in this way it may bepossible to reduce the steaming severity needed to achieve a targetdiffusivity value. In some embodiments, the total amount of oxidemodifier present in the catalyst, as measured on an elemental basis, maybe between about 0.05 and about 20 wt %, and preferably is between about0.1 and about 10 wt %, based on the weight of the final catalyst. Wherethe modifier includes phosphorus, incorporation of modifier into thecatalyst is conveniently achieved by the methods described in U.S. Pat.Nos. 4,356,338; 5,110,776; 5,231,064; and 5,348,643, the entiredisclosures of which are incorporated herein by reference.

The above molecular sieves may be used as the alkylation catalystemployed herein without any binder or matrix, i.e., in so-calledself-bound form. Alternatively, the molecular sieves may be compositedwith another material which is resistant to the temperatures and otherconditions employed in the alkylation reaction. Such materials includeactive and inactive materials and synthetic or naturally occurringzeolites as well as inorganic materials such as clays and/or oxides suchas alumina, silica, silica-alumina, zirconia, titania, magnesia ormixtures of these and other oxides. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Clays may also be included with theoxide type binders to modify the mechanical properties of the catalystor to assist in its manufacture. Use of a material in conjunction withthe molecular sieve, i.e., combined therewith or present during itssynthesis, which itself is catalytically active may change theconversion and/or selectivity of the catalyst. Inactive materialssuitably serve as diluents to control the amount of conversion so thatproducts may be obtained economically and orderly without employingother means for controlling the rate of reaction. These materials may beincorporated into naturally occurring clays, e.g., bentonite and kaolin,to improve the crush strength of the catalyst under commercial operatingconditions and function as binders or matrices for the catalyst. Therelative proportions of molecular sieve and inorganic oxide matrix varywidely, with the sieve content ranging from about 1 to about 90 wt % andmore usually, particularly, when the composite is prepared in the formof beads, in the range of about 2 to about 80 wt % of the composite.

The feeds to the present process comprise an aromatic hydrocarbon feed,comprising benzene and/or toluene, and an alkylating reagent comprisingmethanol and/or dimethyl ether. Any refinery aromatic feed can be usedas the source of the benzene and/or toluene, although in someembodiments it may be desirable to use an aromatic hydrocarbon feedwhich comprises at least 90 wt % toluene. In addition, in someembodiments it may be desirable to pre-treat the aromatic hydrocarbonfeed to remove catalyst poisons, such as nitrogen and sulfur-compounds.

The present alkylation process is conducted at relatively lowtemperatures, namely less than 500° C., such as less than 475° C., orless than 450° C., or less than 425° C., or less than 400° C. In orderto provide commercially viable reaction rates, the process may beconducted at temperatures of at least 250° C., such as least 275° C.,for example least 300° C. In terms of ranges, the process may beconducted at temperatures ranging from 250 to less than 500° C., such asfrom 275 to 475° C., for example from 300 to 450° C.

Operating pressures will vary with temperature but generally are atleast 700 kPa-a, such as at least 1000 kPa-a, for example at least 1500kPa-a, or at least 2000 kPa-a, or at least 3000 kPa-a, or at least 3500kPa-a, up to about 7000 kPa-a, for example up to about 6000 kPa-a, up toabout 5000 kPa-a. In terms of ranges, operating pressures may range from700 kPa-a to 7000 kPa-a, for example from 1000 kPa-a to 6000 kPa-a, suchas from 2000 kPa-a to 5000 kPa-a. In at least some embodiments, bycombining an increased pressure (e.g., a pressure from 200 to 600 oreven closer to 1000 psig) and a decreased temperature (e.g., atemperature from 250-500° C.), the amount of light gases produced in thealkylation reaction may be decreased, and the catalyst aging rate mayalso be decreased (e.g., due to the lower temperatures).

Suitable WHSV values based on total aromatic and alkylating reagentfeeds are in the range from 50 to 0.5 hr′, such as in the range from 10to 1 hr¹. In some embodiments, at least part of the aromatic feed, themethanol alkylating reagent and/or the alkylation effluent may bepresent in the alkylation reaction zone in the liquid phase. As isdescribed in more detail below, alteration of the WHSV may be necessaryin concert with changes in temperature in order to maintain an adequateconversion of benzene, toluene, and/or methanol.

The alkylation reaction can be conducted in any known reactor systemincluding, but not limited to, a fixed bed reactor, a moving bedreactor, a fluidized bed reactor and a reactive distillation unit. Inaddition, the reactor may comprise a single reaction zone or multiplereaction zones located in the same or different reaction vessels. Inaddition, injection of the methanol/dimethyl ether alkylating agent canbe effected at a single point in the reactor or at multiple pointsspaced along the reactor.

The product of the alkylation reaction comprises xylenes, benzene and/ortoluene (both residual and coproduced in the process), C₉₊ aromatichydrocarbons, co-produced water and in some cases unreacted methanol. Itis, however, generally preferred to operate the process so that all themethanol is reacted with the aromatic hydrocarbon feed and thealkylation product is generally free of residual methanol. Thealkylation product is also generally free of light gases generated bymethanol decomposition to ethylene and other olefins. In someembodiments, the organic component of the alkylation product may containat least 80 wt % xylenes.

After separation of the water, the alkylation product may be fed to aseparation section, such as one or more distillation columns, to recoverthe xylenes and separate the benzene and toluene from the C₉₊ aromatichydrocarbon by-products. The resulting benzene and toluene may berecycled to the alkylation reaction zone, while C₉₊ aromatics can berecovered for blending into the gasoline pool or transalkylated withadditional benzene and/or toluene to make additional xylenes.

The xylenes recovered from the alkylation product and any downstream C₉₊transalkylation process may be sent to a paraxylene production loop. Thelatter comprises paraxylene separation section, where paraxylene isconventionally separated by adsorption or crystallization, or acombination of both, and recovered. When paraxylene is separated byadsorption, the adsorbent used preferably contains a zeolite. Typicaladsorbents used include crystalline alumino-silicate zeolites eithernatural or synthetic, such as for example zeolite X, or Y, or mixturesthereof. These zeolites are preferably exchanged by cations such asalkali or alkaline earth or rare earth cations. The adsorption column ispreferably a simulated moving bed column (SMB) and a desorbant, such asfor example paradiethylbenzene, paradifluorobenzene, diethylbenzene, ortoluene, or mixtures thereof, is used to recover the selectivelyadsorbed paraxylene. Commercial SMB units that are suitable for use inthe inventive process are PAREX™ or ELUXYL™.

Reference will now be made to the following non-limiting Example and theaccompany drawings.

EXAMPLE

An experiment was conducted to investigate the alkylation of toluenewith methanol at a temperature of 350° C., a pressure of 600 psig (4238kPa-a) and a WHSV of 3.5 hr⁻¹ based on total feed. The feed usedconsisted of a mixture of methanol and toluene in the weight ratio of1:9. The catalyst used in the study is a formulated MCM-49 extrudate(80% weight ratio of 1:9. The catalyst used in the study is a formulatedMCM-49 extrudate (80% zeolite/20% alumina binder). The reaction wascarried out in a down flow fixed bed reactor. The liquid product wascollected and analyzed by a 6890 Agilent GC. The gas yield wascalculated by difference. The results are summarized in FIGS. 1 and 2.

As can be seen from FIG. 1, methanol conversion is essentially 100%. Nomethanol was detected in the product throughout the run. Tolueneconversion is stable over the eight day test. Average toluene conversionis 30%, consistent with the feed composition.

Selectivity observed in the experiment is summarized in FIG. 2, fromwhich it will be seen that the average xylene selectivity over the eightday test is at or near 80 wt %. C₉₊ selectivity is about 20 wt %.Benzene selectivity is about 1.5 wt %. The gas make is estimated to be0.5 wt %.

Example 2

Further experiments were conducted using the catalyst and reactor designdiscussed above in Example 1. The feed in each of these experiments wasa mixture of methanol and toluene with a methanol:toluene mole ratio of1:3. During the experiments various conditions (e.g., temperature,pressure, WHSV, etc.) were varied to determine their effect on thealkylation reaction. The results of these experiments is shown below inTable 1.

TABLE 1 Sample 1 2 3 4 5 Pressure (psig) 600 600 600 600 200 Temperature(° C.) 275 300 350 350 350 WHSV (hr⁻¹) 3.45 3.45 3.45 10.04 3.45 YieldsMethanol 94.11 98.09 100.00 97.91 95.27 Conversion (%) Toluene 0.0219.49 29.33 21.18 7.55 Conversion (%) Xylene 93.80 87.81 83.18 87.1278.46 Selectivity (%) Para-Xylene 59.34 55.47 26.79 63.74 41.07Selectivity (%)

Referring to Samples 1, 2, and 3, it can be seen that at a constant WHSV(i.e., at 3.45 hr¹), increasing temperature from (275° C. to 300° C. to350° C., respectively) results in an expected drop in xylene andpara-xylene selectivity, but a surprisingly large increase in bothtoluene and methanol conversion rates. When the reaction temperature isreduced below 250° C., conversion rates (e.g., for methanol and/ortoluene) drop to such a degree such that useful production of xylenesand para-xylenes becomes unfeasible.

In addition, referring to Samples 2 and 4, when the toluene and methanolconversion is held more or less constant by increasing WHSV velocity, anincreasing temperature causes a surprisingly large increase inpara-xylene selectivity while overall xylene selectivity remainsrelatively constant.

Finally, referring to Samples 3 and 5, it can be seen that an increasein pressure from 200 psig (1379 kPa-g) to 600 psig (4137 kPa-g) appearsto result in a lower para-xylene selectivity, but a substantially highertoluene conversion along with increased methanol conversion and overallxylene selectivity. Thus, in at least some embodiments, coupling anincreased reaction pressure (e.g., above 200 psig) with a temperaturebetween 250° C. and 500° C. appears to result in favorable para-xyleneyields and feed conversion rates.

All patents, test procedures, and other documents cited herein,including priority documents, are fully incorporated by reference to theextent such disclosure is not inconsistent and for all jurisdictions inwhich such incorporation is permitted.

While the illustrative forms disclosed herein have been described withparticularity, it will be understood that various other modificationswill be apparent to and can be readily made by those skilled in the artwithout departing from the spirit and scope of the disclosure.Accordingly, it is not intended that the scope of the claims appendedhereto be limited to the example and descriptions set forth herein, butrather that the claims be construed as encompassing all the features ofpatentable novelty which reside herein, including all features whichwould be treated as equivalents thereof by those skilled in the art towhich this disclosure pertains.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

1. A process for producing paraxylene, the process comprising: (a)contacting an aromatic hydrocarbon feed comprising toluene with analkylating reagent comprising methanol and/or dimethyl ether in at leastone alkylation reaction zone in the presence of an alkylation catalystfree of hydrogenation metals and rare-earth metals and comprising amolecular sieve having a Constraint Index less than 5 and underalkylation conditions comprising a temperature less than 500° C. and apressure of 700 kPa-a to 7000 kPa-a to produce an alkylated aromaticproduct comprising xylenes, wherein the at least one alkylation reactionzone comprises a fixed bed of the alkylation catalyst; and (b)recovering paraxylene from the alkylated aromatic product.
 2. Theprocess of claim 1, wherein the aromatic hydrocarbon feed comprises atleast 90 wt % toluene.
 3. The process of claim 2, wherein the alkylatingreagent comprises methanol.
 4. The process of claim 3, wherein thealkylation conditions comprise a temperature of at least 250° C.
 5. Theprocess of claim 4, wherein the alkylation conditions comprise atemperature from 250° C. to 450° C.
 6. The process of claim 5, whereinthe alkylation conditions comprise a pressure from 3000 kPa-a to 7000kPa-a.
 7. The process of claim 6, wherein the alkylation conditionscomprise a weight hourly space velocity based on the aromatichydrocarbon feed of 50 to 0.5 hr⁻¹.
 8. The process of claim 7, whereinthe alkylated aromatic product comprises at least 80 wt % xylenes. 9.The process of claim 8, wherein the alkylation catalyst comprises atleast one molecular sieve of the MWW framework structure.
 10. Theprocess of claim 9, wherein the alkylation catalyst comprises at leastone molecular sieve selected from the group consisting of MCM-22, PSH-3,SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, EMM-10, EMM-12,EMM-13, UZM-8, UZM-8HS, UZM-37, MIT-1, and mixtures thereof.
 11. Theprocess of claim 10, wherein the alkylation catalyst comprises MCM-49.12. A process for producing paraxylene, the process comprising: (a)contacting an aromatic hydrocarbon feed comprising toluene with analkylating reagent comprising methanol in at least one alkylationreaction zone in the presence of an alkylation catalyst free ofhydrogenation metals and rare-earth metals and comprising a molecularsieve of the MWW framework structure and under alkylation conditionscomprising a temperature from about 250° C. to less than about 500° C.and a pressure of 700 kPa-a to 7000 kPa-a to produce an alkylatedaromatic product comprising xylenes, wherein the at least one alkylationreaction zone comprises a fixed bed of the alkylation catalyst; and (b)recovering paraxylene from the alkylated aromatic product.
 13. Theprocess of claim 12, wherein the aromatic hydrocarbon feed comprises atleast 90 wt % toluene.
 14. The process of claim 13, wherein thealkylation conditions comprise a temperature from 250° C. to 450° C. 15.The process of claim 14, wherein the alkylation conditions comprise apressure from 3000 kPa-a to 7000 kPa-a.
 16. The process of claim 15,wherein the alkylation conditions comprise a weight hourly spacevelocity based on the aromatic hydrocarbon feed of 50 to 0.5 hr⁻¹. 17.The process of claim 16, wherein the alkylated aromatic productcomprises at least 80 wt % xylenes.
 18. The process of claim 17, whereinthe alkylation catalyst comprises at least one molecular sieve of theMWW framework structure.
 19. The process of claim 18, wherein thealkylation catalyst comprises at least one molecular sieve selected fromthe group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2,MCM-36, MCM-49, MCM-56, EMM-10, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37,MIT-1, and mixtures thereof.
 20. The process of claim 19, wherein thealkylation catalyst comprises MCM-49.